EP0231415B1 - Sealing, consolidating and/or binding agent based on modified alcaline silicate solutions - Google Patents

Sealing, consolidating and/or binding agent based on modified alcaline silicate solutions Download PDF

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Publication number
EP0231415B1
EP0231415B1 EP86101482A EP86101482A EP0231415B1 EP 0231415 B1 EP0231415 B1 EP 0231415B1 EP 86101482 A EP86101482 A EP 86101482A EP 86101482 A EP86101482 A EP 86101482A EP 0231415 B1 EP0231415 B1 EP 0231415B1
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EP
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Prior art keywords
solution
preparations
sealing
glyoxal
metaborate
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EP86101482A
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German (de)
French (fr)
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EP0231415A1 (en
Inventor
Wolfgang Dr. Friedemann
Wolfgang Pesch
Kurt Feulner
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to EP86101482A priority Critical patent/EP0231415B1/en
Priority to AT86101482T priority patent/ATE51392T1/en
Priority to DE8686101482T priority patent/DE3669871D1/en
Priority to ES8700248A priority patent/ES2003677A6/en
Priority to US07/011,174 priority patent/US4755226A/en
Publication of EP0231415A1 publication Critical patent/EP0231415A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • C09K17/42—Inorganic compounds mixed with organic active ingredients, e.g. accelerators
    • C09K17/46—Inorganic compounds mixed with organic active ingredients, e.g. accelerators the inorganic compound being a water-soluble silicate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S106/00—Compositions: coating or plastic
    • Y10S106/90—Soil stabilization

Definitions

  • the invention relates to agents based on modified alkali metal silicate solutions for sealing and / or solidifying and / or binding, the use of these agents and a method for sealing and / or solidifying and / or binding using these agents.
  • aqueous alkali metal silicate solutions have long been known and are widely used in practice, e.g. solidifying and sealing soil and soil.
  • alkali metal silicate solutions are injected into the ground during tunnel construction or underground construction in order to solidify the ground and, if necessary, to undertake buildings that have already been erected and to consolidate the ground.
  • the aqueous alkali metal silicate solutions can be used to solidify building materials and masonry as well as binders for bodies made of minerals.
  • alkali metal silicate solutions are used without additives, they often cannot meet the technical requirements. Hardness, elasticity and resistance to temperature and water are often poor. Therefore, numerous proposals have been made to improve the properties of the alkali metal silicate solutions.
  • Various types of hardeners have been used in particular, e.g. Glyoxal or dicarboxylic acid ester.
  • FR-PS 1 166 581 describes the use of glyoxal as a hardener for alkali metal silicate solutions.
  • glyoxal as a hardener for alkali metal silicate solutions.
  • the rapid reaction between concentrated alkali metal silicate solutions and the glyoxal severely limits the possible applications.
  • EP-A 0 028 495 describes agents for soil stabilization which contain aqueous alkali metal silicate solutions, glyoxal and hydrogen peroxide and, if appropriate, inorganic salts.
  • Suitable inorganic salts are those of groups I to 111, in particular sodium aluminate, aluminum chloride, copper sulfate, zinc chloride and calcium chloride, calcium chloride being preferred.
  • DE-OS 2 242 713 describes a method for stabilizing and solidifying soils with the aid of an aqueous silicate solution with the addition of a gel-forming agent.
  • the disadvantage of these agents is that after the introduction of such agents into the soil, groundwater and soil are contaminated with large amounts of organic substances that have to be broken down. This type of exposure is measured as "chemical oxygen demand (COD value).
  • DE-OS 2 714 889 describes binders based on alkali metal silicate solutions with a shortened setting time and improved water resistance. These binders based on alkali metal silicate solutions with a molar ratio Si0 2 : Me 2 0 in the range from 1.8 to 4.0 and a solids content of 20 to 55% by weight are characterized by a content of potassium metaborate, the molar ratio Si0 2 : Potassium metaborate ranges from 0.1 to 50.
  • the advantages to be achieved with these binders ie the high water resistance and in particular the increased setting speed, cannot be achieved with sodium metaborate, as can be seen from example 1 and the comparative examples E and F of DE-OS 2 714 889 described therein.
  • the object of the present invention is to eliminate the stated disadvantages of the prior art by modifying the alkali metal silicate solutions and, in particular, to provide alkali metal silicate solutions which have sufficiently long gelling times and curing times for practice and application, even at high solids contents.
  • the task is solved by providing means for sealing, solidifying and binding on the basis of modified alkali metal silicate solutions.
  • the invention relates to compositions for sealing and / or solidifying and / or binding on the basis of modified alkali metal silicate solutions, which are characterized in that they contain alkali metal silicate solutions with a molar ratio Si0 2 : Me 2 0, where Me is sodium or potassium, from 2 to 4,5, sodium metaborate and / or potassium metaborate in a molar ratio Si0 2 : B 2 0 3 from 5 to 400 and glyoxal.
  • the agents according to the present invention which contain alkali metal silicate solutions in combination with sodium metaborate and / or potassium metaborate and with glyoxal also in high solids contents lead to delays in setting, ie that the combination of two water glass hardeners or accelerators causes a hardening delay.
  • the agents according to the invention have an increased gelation time and hardening time even at high solids contents.
  • the agents according to the invention preferably contain alkali metal silicates with SiO 2 : Me 2 0 molar ratios of 3.0 to 4.0.
  • the Si0 2 : B 2 0 3 molar ratio is preferably 7 to 60.
  • the glyoxal is used in the compositions according to the invention in amounts of 0.4% by weight to 12% by weight, preferably from 1.5% by weight to 7% by weight.
  • Technical quality glyoxal is preferably used.
  • a technical quality glyoxal is e.g. the product Glyfixe CS 50 from Hoechst.
  • the SiO 2 concentration of the ready-to-use silicate solutions is at most 30% by weight.
  • the agents according to the invention can be used to seal or solidify sandy soils.
  • the agents according to the invention are suitable for sealing and / or solidifying mineral building materials, e.g. of concrete, of mineral slabs and also of masonry.
  • agents according to the invention are also suitable as binders for mineral moldings, such as those e.g. used in foundries.
  • the invention also relates to the use of the agents according to the invention for sealing and / or consolidating floors, for sealing and / or consolidating mineral building materials such as concrete, masonry, mineral slabs and the like and for binding mineral shaped articles.
  • the invention relates to methods for sealing and / or solidifying floors, mineral building materials and for binding mineral moldings, the methods being characterized in that the agents according to the invention are used.
  • the gel time of the finished injection solution and the degree of solidification of the injected soils are the benchmark for the quality and applicability of the products. In the following examples, these criteria were therefore determined and compared with the practical requirements (gel time 30 to 60 min, compressive strength ⁇ 200 N / cm2).
  • the gelling time was determined with 100 ml solution for injection in a poly beaker at room temperature, without cooling, on a magnetic stirrer with setting 3, the time until the stirring bar came to a standstill due to the onset of gelling.
  • the pressure resistance of the test specimens was determined using a test apparatus according to Georg Fischer AG, PO Box 689, CH-8201 Schaffhausen.
  • the marketable water glass solutions were sodium water glass HK30, with an Si0 2 content of 22.01% and an Na 2 0 content of 5.67%, a density of 1261 kg / m 3 (at 20 ° C ), a viscosity of 18 mPas (20 ° C) and a molar ratio Si0 2 : Na 2 0 of 4.0 and sodium water glass 37/40 with an Si0 2 content of 26.66%, an Na 2 0 content of 7 , 94%, a density of 1349 kg / m 3 (20 ° C), a viscosity of 56 mPas (20 ° C) and a molar ratio of SiO 2 : Na 2 O of 3.46.
  • the gelling time measured with a magnetic stirrer, was 40 min, the compressive strength of the test specimen was 207 N / cm 2 .
  • a metaborate-free batch resulted in: 900 ml HK 30 sodium water glass, mixed with 50 ml softened water and 50 ml of a 40% glyoxal solution, measured with a magnetic stirrer, a gelling time of 21 min and a pressure resistance of the test specimen of 202 N / cm 2 .
  • the metaborate-free solution for injection did not have a gelation time that was sufficient in practice.
  • the gelling time measured with a magnetic stirrer, was 43 min, the compressive strength of the test specimen was 272 N / cm2.
  • the metaborate-free mixture of 700 ml of 37/40 sodium water glass, 220 ml of softened water and 80 ml of the 40% glyoxal solution gave a gel time of 16 min and a compressive strength of the test specimen of 251 N / cm 2 .
  • the gelling time for this metaborate-free injection solution was not sufficient for practical purposes.
  • the gelling time was 44 min, the compressive strength of the test specimen was 205 W / cm 2 .
  • the gel time of the metaborate-free injection solution was not sufficient for practical purposes.
  • the gelling time was 39 min and the compressive strength of the test specimen was 264 N / cm 2 .
  • the gelling time is not sufficient for practical applications.
  • the gel time of this injection solution was 42 min, the compressive strength of the test specimen was 260 N / cm 2 .
  • the gel time was 37 min, the compressive strength of the test specimen was 262 N / cm 2 .
  • the gel time of this solution was 45 min, the compressive strength of the test specimen was 204 N / cm 2 .
  • the gel time of this injection solution was 20 min and was therefore not sufficient for practical use.
  • the gel time was 21 minutes and was therefore not sufficient for practical use. A test specimen could not be produced because only soft gel was produced.
  • the gel time of the injection solution was 14 min and was therefore not sufficient for practical use.
  • composition of the injection solutions used was chosen so that comparable gel times and strengths of the test specimens resulted.
  • the values obtained are shown in the following table.
  • the COD values obtained show that the use of the injection solution according to the invention leads to significantly lower values - and thus to a significantly lower contamination of the groundwater or the soil - than the use of injection solutions according to the prior art.
  • Potassium water glass 28/30 with an SiO 2 content of 21.04%, a K 2 0 content of 8.23%, a density of 1256 kg / m 3 and a viscosity of 44 mPas was used for Examples 8 to 11 . Density and viscosity were measured at 20 ° C, the molar ratio Si0 2 : K 2 0 was 4.01.
  • the gelling time was 210 min.
  • This solution for injection had a gel time of 8 hours and can therefore be used fully during a work shift.
  • the metaborate-free injection solution made from 120 g 28/30 potassium water glass, 73 g softened water, and 7 g technical glyoxal solution (Glyfix CS 50 from Hoechst France) has a gel time of 40 min.
  • silicate binders in foundries.
  • a binder is desired which has open times in the premix that are as long as possible, but which can occasionally be less than 30 minutes.
  • 100 g of sodium water glass 48/50 were mixed with 10 g of softened water, 4.1 g of potassium metaborate and 13.4 g of a technical glyoxal solution (Glyfix CS 50 from Hoechst France) to 127.5 g of binder with 26.2% SiO 2 and 1.39% B 2 0 3 .
  • the binder had a molar ratio Si0 2 : B 2 0 3 of 21.9.
  • the GE time was 10 min.
  • the metaborate-free binder from 100 g soda water glass 48/50, 10 g softened water and 13.4 g technical glyoxal solution (Glyfix CS 50 from Hoechst France) only gave a gel time of 5.5 min.
  • 100 g of soda water glass 43/45 were mixed with 10 g of softened water, 8.2 g of potassium metaborate and 12 g of a technical glyoxal solution (Glyfix CS 50 from Hoechst France) to 130.2 g of binder with 24.1% Si0 2 and 2 , 67% B 2 0 3 .
  • the binder had a molar ratio Si0 2 : B 2 0 3 of 10.5 and a gel time of 18 min.
  • a metaborate-free batch consisting of 100 g of sodium water glass 43/45, 10 g of softened water and 12 g of technical glyoxal (Glyfix CS 50 from Hoechst France) gave a gel time of 5.5 min.
  • the metaborate-free batch consisting of 100 g of 43/45 sodium water glass, 5 g of softened water and 14.1 g of technical glyoxal solution (Glyfix CS 50 from Hoechst France) gave a gel time of 3.5 min.

Abstract

Sealing and/or stabilizing and/or binding preparations comprising modified alkali metal silicate solutions having a molar ratio of SiO2 to Me2O of from 2 to 4.5 wherein Me represents sodium or potassium; sodium metaborate and/or potassium metaborate in a molar ratio of SiO2 to B2O3 of from 5 to 400; and glyoxal, and to the use of these preparations.

Description

Die Erfindung betrifft Mittel auf der Basis von modifizierten Alkalimetallsilikatlösungen zum Abdichten und/oder Verfestigen und/oder zum Binden, die Anwendung dieser Mittel sowie ein Verfahren zum Abdichten und/oder Verfestigen und/oder zum Binden unter Einsatz dieser Mittel.The invention relates to agents based on modified alkali metal silicate solutions for sealing and / or solidifying and / or binding, the use of these agents and a method for sealing and / or solidifying and / or binding using these agents.

Mittel auf der Basis von wässrigen Alkalimetallsilikatlösungen sind seit langem bekannt und werden in großem Umfang in der Praxis eingesetzt, z.B. beim Verfestigen und Abdichten von Erdreich und von Böden. Beispielsweise werden Alkalimetallsilikatlösungen beim Tunnelbau oder beim U-Bahnbau in das Erdreich injiziert, um den Boden zu verfestigen und gegebenenfalls bereits errichtete Gebäude zu unterfangen und das Erdreich zu verfestigen. Weiterhin können die wässrigen Alkalimetallsilikatlösungen zum Verfestigen von Baustoffen und Mauerwerk sowie als Bindemittel für aus Mineralien bestehende Körper verwendet werden.Agents based on aqueous alkali metal silicate solutions have long been known and are widely used in practice, e.g. solidifying and sealing soil and soil. For example, alkali metal silicate solutions are injected into the ground during tunnel construction or underground construction in order to solidify the ground and, if necessary, to undertake buildings that have already been erected and to consolidate the ground. Furthermore, the aqueous alkali metal silicate solutions can be used to solidify building materials and masonry as well as binders for bodies made of minerals.

Werden Alkalimetallsilikatlösungen ohne Zusätze verwendet, so können sie die technischen Anforderungen oft nich erfüllen. So sind Härte, Elastizität und Beständigkeit gegen Temperaturen und Wasser häufig mangelhaft. Daher sind schone Zahlreiche Vorschläge gemacht worden, um die Eigenschaften der Alkalimetallsilikatlösungen zu verbessern. Insbesondere wurden Härter verschiedenster Art eingesetzt, wie z.B. Glyoxal oder Dicarbonsäureester.If alkali metal silicate solutions are used without additives, they often cannot meet the technical requirements. Hardness, elasticity and resistance to temperature and water are often poor. Therefore, numerous proposals have been made to improve the properties of the alkali metal silicate solutions. Various types of hardeners have been used in particular, e.g. Glyoxal or dicarboxylic acid ester.

Die FR-PS 1 166 581 beschreibt die Verwendung von Glyoxal als Härter für Alkalimetallsilikatlösungen. Die rasche Reaktion zwischen konzentrierten Alkalimetallsilikatlösungen und dem Glyoxal grenzen die Anwendungsmöglichkeiten jedoch stark ein.FR-PS 1 166 581 describes the use of glyoxal as a hardener for alkali metal silicate solutions. However, the rapid reaction between concentrated alkali metal silicate solutions and the glyoxal severely limits the possible applications.

Es ist ferner bekannt, die Reaktionsgeschwindigkeiten der Alkalimetallsilikatlösungen, die Härter enthalten, durch Verdünnen mit Wasser, d.h. durch Absenken der Feststoffgehalte, im gewünschten Maße zu verlängern. Damit ergibt sich jedoch der Nachteil, daß beispielsweise die Verfestigung von Böden und/oder mineralischen Baustoffen und Formstoffen nicht ausreichend erfolgt und dadurch wiederum die Anwendungsmöglichkeiten stark eingeschränkt werden.It is also known to reduce the reaction rates of alkali metal silicate solutions containing hardeners by dilution with water, i.e. by lowering the solids content to extend it to the desired extent. However, this has the disadvantage that, for example, the consolidation of soils and / or mineral building materials and molding materials does not take place sufficiently, and this in turn severely limits the possible applications.

Die EP-A 0 028 495 beschreibt Mittel zur Bodenverfestigung, die wässrige Alkalimetallsilikatlösungen, Glyoxal und Wasserstoffperoxid sowie gegebenenfalls anorganische Salze enthalten. Als anorganische Salze kommen solche der Gruppen I bis 111 in Frage, insbesondere Natriumaluminat, Aluminiumchlorid, Kupfersulfat, Zinkchlorid und Kalziumchlorid, wobei Kalziumchlorid bevorzugt ist. Durch Verfestigung des Erdreiches mit diesen Mitteln wird jedoch eine befriedigende Druckfestigkeit nicht erreicht.EP-A 0 028 495 describes agents for soil stabilization which contain aqueous alkali metal silicate solutions, glyoxal and hydrogen peroxide and, if appropriate, inorganic salts. Suitable inorganic salts are those of groups I to 111, in particular sodium aluminate, aluminum chloride, copper sulfate, zinc chloride and calcium chloride, calcium chloride being preferred. By consolidating the soil with these agents, however, a satisfactory compressive strength is not achieved.

In der DE-OS 2 242 713 wird ein Verfahren zum Stabilisieren und Verfestigen von Böden mit Hilfe einer wässrigen Silikatlösung unter Zusatz eines gelbildenden Mittels beschrieben. Als gelbildendes Mittel dient hierbei ein Gemisch aus Bernsteinsäuredialkylester mit Dialkylestern homologer höherer Carbonsäuren, wie Glutarsäure und/oder Adipinsäure. Nachteil dieser Mittel ist jedoch, daß nach dem Einbringen solcher Mittel in den Boden Grundwässer und Boden mit großen Mengen an organischen Substanzen belastet werden, die abgebaut werden müssen. Diese Art der Belastung wird als "chemischer Sauerstoffbedarf (CSB-Wert) gemessen.DE-OS 2 242 713 describes a method for stabilizing and solidifying soils with the aid of an aqueous silicate solution with the addition of a gel-forming agent. A mixture of dialkyl succinate with dialkyl esters of homologous higher carboxylic acids, such as glutaric acid and / or adipic acid, serves as the gel-forming agent. However, the disadvantage of these agents is that after the introduction of such agents into the soil, groundwater and soil are contaminated with large amounts of organic substances that have to be broken down. This type of exposure is measured as "chemical oxygen demand (COD value).

Die DE-OS 2 714 889 beschreibt Bindemittel auf Basis von Akalimetallsilikatlösungen mit verkürzter Abbindezeit und verbesserter Wasserfestigkeit. Diese Bindemittel auf der Basis von Alkalimetallsilikatlösungen mit einem Molverhältnis Si02 : Me20 im Bereich von 1,8 bis 4,0 und einem Feststoffgehalt von 20 bis 55 Gew.-% sind durch einen Gehalt an Kaliummetaborat gekennzeichnet, wobei das Molverhältnis Si02 : Kaliummetaborat im Bereich von 0,1 bis 50 liegt. Die mit diesen Bindemitteln zu erzielenden Vorteile, d.h. die hohe Wasserbeständigkeit and insbesondere die erhöhte Abbindegeschwindigkeit, lassen sich jedoch nicht mit Natriummetaborat erzielen, wie aus Beispiel 1 und den darin beschriebenen Vergleichsbeispielen E und F der DE-OS 2 714 889 hervorgeht.DE-OS 2 714 889 describes binders based on alkali metal silicate solutions with a shortened setting time and improved water resistance. These binders based on alkali metal silicate solutions with a molar ratio Si0 2 : Me 2 0 in the range from 1.8 to 4.0 and a solids content of 20 to 55% by weight are characterized by a content of potassium metaborate, the molar ratio Si0 2 : Potassium metaborate ranges from 0.1 to 50. However, the advantages to be achieved with these binders, ie the high water resistance and in particular the increased setting speed, cannot be achieved with sodium metaborate, as can be seen from example 1 and the comparative examples E and F of DE-OS 2 714 889 described therein.

Aufgabe der vorliegenden Erfindung ist es, durch Modifizierung der Alkalimetallsilikatlösungen die angegebenen Nachteile des Standes der Technik zu beseitigen und insbesondere Alkalimetallsilikatlösungen zur Verfügung zu stellen, die für die Praxis und Anwendung ausreichend lange Gelierzeiten und Härtungszeiten auch bei hohen Feststoffgehalten aufweisen.The object of the present invention is to eliminate the stated disadvantages of the prior art by modifying the alkali metal silicate solutions and, in particular, to provide alkali metal silicate solutions which have sufficiently long gelling times and curing times for practice and application, even at high solids contents.

Gelöst wird die Aufgabe durch zur Verfügung stellen von Mitteln zum Abdichten, Verfestigen und Binden auf der Basis von modifizierten Alkalimetallsilikatlösungen.The task is solved by providing means for sealing, solidifying and binding on the basis of modified alkali metal silicate solutions.

Die Erfindung betrifft Mittel zum Abdichten und/oder Verfestigen und/oder zum Binden auf der Basis von modifizierten Alkalimetallsilikatlösungen, die dadurch gekennzeichnet sind, daß sie Alkalimetallsilikatlösungen mit einem Molverhältnis Si02 : Me20, wobei Me Natrium oder Kalium bedeutet, von 2 bis 4,5, Natriummetaborat und/oder Kaliummetaborat in einem Molverhältnis Si02 : B203 von 5 bis 400 und Glyoxal enthalten.The invention relates to compositions for sealing and / or solidifying and / or binding on the basis of modified alkali metal silicate solutions, which are characterized in that they contain alkali metal silicate solutions with a molar ratio Si0 2 : Me 2 0, where Me is sodium or potassium, from 2 to 4,5, sodium metaborate and / or potassium metaborate in a molar ratio Si0 2 : B 2 0 3 from 5 to 400 and glyoxal.

Gegenüber dem Stand der Technik - gemäß der FR-PS 1166 581 und der DE-OS 2 714 889 - ist es überraschend, daß die Mittel gemäß vorliegender Erfindung, die Alkalimetallsilikatlösungen in Kombination mit Natriummetaborat und/oder Kaliummetaborat und mit Glyoxal enthalten, auch bei hohen Feststoffgehalten zu Abbindeverzögerungen führen, d.h., daß die Kombination zweier Wasserglashärter bzw. -beschleuniger eine Härtungsverzögerung bewirkt. Die erfindungsgemäßen Mittel weisen eine erhöhte Gelierzeit und Härtungszeit auch bei hohen Feststoffgehalten auf.Compared to the prior art - according to FR-PS 1166 581 and DE-OS 2 714 889 - it is surprising that the agents according to the present invention which contain alkali metal silicate solutions in combination with sodium metaborate and / or potassium metaborate and with glyoxal also in high solids contents lead to delays in setting, ie that the combination of two water glass hardeners or accelerators causes a hardening delay. The agents according to the invention have an increased gelation time and hardening time even at high solids contents.

Weder der Einsatz von Glyoxal alleine, noch der Einsatz von Alkalisierungsmitteln, wie z.B. Natriumhydroxid, Kaliumhydroxid oder Aminen, noch von anderen Boraten, wie z.B. Kaliumtetraborat, ergaben den gewünschten Effekt, wie aus den später folgenden Vergleichsbeispielen hervorgeht.Neither the use of glyoxal alone, nor the use of alkalizing agents such as sodium hydroxide, potassium hydroxide or amines, or other borates, such as potassium tetraborate, gave the desired effect, as can be seen from the comparative examples that follow.

Bevorzugt enthalten die Mittel gemäß der Erfindung Akalimetallsilikate mit Si02 : Me20 Molverhältnissen von 3,0 bis 4,0.The agents according to the invention preferably contain alkali metal silicates with SiO 2 : Me 2 0 molar ratios of 3.0 to 4.0.

In den Mitteln gemäß der Erfindung beträgt das Si02 : B203 Molverhältnis vorzugsweise 7 bis 60.In the agents according to the invention, the Si0 2 : B 2 0 3 molar ratio is preferably 7 to 60.

Das Glyoxal wird in Mengen von 0,4 Gew.-% bis 12 Gew.-%, vorzugsweise von 1,5 Gew.-% bis 7 Gew.-% in den erfindungsgemäßen Mitteln verwendet. Vorzugsweise wird Glyoxal technischer Qualität verwendet. Ein Glyoxal technischer Qualität ist z.B. das Produkte Glyfixe CS 50 der Firma Hoechst.The glyoxal is used in the compositions according to the invention in amounts of 0.4% by weight to 12% by weight, preferably from 1.5% by weight to 7% by weight. Technical quality glyoxal is preferably used. A technical quality glyoxal is e.g. the product Glyfixe CS 50 from Hoechst.

In den Mitteln gemäß der Erfindung beträgt die Si02- Konzentration der anwendungsfertigen Silikatlösungen maximal 30 Gew.-%.In the agents according to the invention, the SiO 2 concentration of the ready-to-use silicate solutions is at most 30% by weight.

Die erfindungsgemäßen Mittel können zum Abdichten oder Verfestigen von sandigen Böden verwendet werden.The agents according to the invention can be used to seal or solidify sandy soils.

Ferner eignen sich die erfindungsgemäßen Mittel zum Abdichten und/oder Verfestigen von mineralischen Baustoffen, wie z.B. von Beton, von mineralischen Platten und auch von Mauerwerk.Furthermore, the agents according to the invention are suitable for sealing and / or solidifying mineral building materials, e.g. of concrete, of mineral slabs and also of masonry.

Schließlich eignen sich die erfindungsgemäßen Mittel auch als Bindemittel für mineralische Formkörper, wie sie z.B. in Gießereien verwendet werden.Finally, the agents according to the invention are also suitable as binders for mineral moldings, such as those e.g. used in foundries.

Die Erfindung betrifft dementsprechend auch die Verwendung der erfindungsgemäßen Mittel zum Abdichten und/oder Verfestigen von Böden, zum Abdichten und/oder Verfestigen von mineralischen Baustoffen wie Beton, Mauerwerk, mineralischen Platten und dergleichen und zum Binden für mineralische Formkörper.Accordingly, the invention also relates to the use of the agents according to the invention for sealing and / or consolidating floors, for sealing and / or consolidating mineral building materials such as concrete, masonry, mineral slabs and the like and for binding mineral shaped articles.

Weiterhin betrifft die Erfindung Verfahren zum Abdichten und/oder Verfestigen von Böden, von mineralischen Baustoffen und zum Binden von mineralischen Formkörpern, wobei die Verfahren dadurch gekennzeichnet sind, daß man die erfindungsgemäßen Mittel einsetzt.Furthermore, the invention relates to methods for sealing and / or solidifying floors, mineral building materials and for binding mineral moldings, the methods being characterized in that the agents according to the invention are used.

Gegenüber der Verwendung von Härtergemischen nach dem Stand der Technik - wie sie beispielsweise in der DE-OS 2 242 713 beschrieben sind - ergeben sich bei der Verwendung der erfindungsgemäßen Mittel deutlich geringere Belastungen des Erdreichs und der Böden und damit auch des Grundwassers mit organischen Bestandteilen. Dies drückt sich durch stark herabgesetzte Werte des chemischen Sauerstoffbedarfs (CSB-Wert) aus (siehe Vergleichsbeispiel 4).Compared to the use of hardener mixtures according to the prior art - as described for example in DE-OS 2 242 713 - the use of the agents according to the invention results in significantly lower loads on the soil and the soil and thus also on the groundwater with organic constituents. This is expressed by greatly reduced values of the chemical oxygen demand (COD value) (see comparative example 4).

Die Erfindung wird durch die folgenden Beispiele erläutert.The invention is illustrated by the following examples.

I Zur Bodenverfestigung durch SilikatgelijektionenI For soil stabilization using silicate gel injections

Bei der Silikatgelinjektion sind die Gelierzeit der fertigen Injektionslösung und der Verfestigungsgrad der injizierten Böden Maßstab für die Qualität und Anwendbarkeit der Produkte. Bei den folgenden Beispielen wurden deshalb diese Kriterien bestimmt, und mit den Anforderungen der Praxis (Gelzeit 30 bis 60 min, Druckfestigkeit ≥ 200 N/cm2) verglichen. Die Bestimmung der Gelierzeit erfolgte mit 100 ml Injektionslösung in einem Polybecher bei Raumtemperatur, ohne Kühlung, auf einem Magnetrührer mit der Einstellung Stufe 3, gemessen wurde die Zeit bis zum Stillstand des Rührstabes durch die einsetzende Gelierung.In silicate gel injection, the gel time of the finished injection solution and the degree of solidification of the injected soils are the benchmark for the quality and applicability of the products. In the following examples, these criteria were therefore determined and compared with the practical requirements (gel time 30 to 60 min, compressive strength ≥ 200 N / cm2). The gelling time was determined with 100 ml solution for injection in a poly beaker at room temperature, without cooling, on a magnetic stirrer with setting 3, the time until the stirring bar came to a standstill due to the onset of gelling.

Zur Prüfung der Druckfestigkeit wurden 200 g trockener Quarzsand F32 zu zylindrischen Prüfkörpem (Durchmesser 50 mm, Höhe 60 mm) verdichtet (Dichte 1,7 g/cm3). Anschließend wurde die Injektionslösung von unten eingepreßt, bis der Flüssigkeitsspiegel die Prüfkörperoberfläche erreicht hatte. Nach Härtung der Prüfkörper (5 Stunden) wurden sie ausgeschalt und in einem luftdicht verschlossenen Kunststoffbecher 7 Tage bei Raumtemperatur (21 bis 22°C) bis zur Prüfung der Druckfestigkeit belassen.To test the compressive strength, 200 g of dry F32 quartz sand was compressed into cylindrical test specimens (diameter 50 mm, height 60 mm) (density 1.7 g / cm3). The solution for injection was then injected from below until the liquid level reached the test specimen surface. After the test specimens had hardened (5 hours), they were switched off and left in an airtight plastic cup for 7 days at room temperature (21 to 22 ° C.) until the compressive strength was tested.

Die Ermittlung der Druckfestigkeit der Prüfkörper erfolgte mit einer Prüfapparatur nach Georg Fischer AG, Postfach 689, CH-8201 Schaffhausen.The pressure resistance of the test specimens was determined using a test apparatus according to Georg Fischer AG, PO Box 689, CH-8201 Schaffhausen.

Für die Beispiele 1 bis 7 wurden die marktgängigen Wasserglaslösungen Natronwasserglas HK30, mit einem Si02-Gehalt von 22,01 % und einem Na20-Gehalt von 5,67 %, einer Dichte von 1261 kg/m3 (bei 20°C), einer Viskosität von 18 mPas (20°C) und einem Molverhältnis Si02 : Na20 von 4,0 sowie Natronwasserglas 37/40 mit einem Si02-Gehalt von 26,66 %, einem Na20-Gehalt von 7,94 %, einer Dichte von 1349 kg/m3 (20°C), einer Viskosität von 56 mPas (20°C) und einem Mol-Verhältnis SiO2 : Na2O von 3,46 eingesetzt.For examples 1 to 7, the marketable water glass solutions were sodium water glass HK30, with an Si0 2 content of 22.01% and an Na 2 0 content of 5.67%, a density of 1261 kg / m 3 (at 20 ° C ), a viscosity of 18 mPas (20 ° C) and a molar ratio Si0 2 : Na 2 0 of 4.0 and sodium water glass 37/40 with an Si0 2 content of 26.66%, an Na 2 0 content of 7 , 94%, a density of 1349 kg / m 3 (20 ° C), a viscosity of 56 mPas (20 ° C) and a molar ratio of SiO 2 : Na 2 O of 3.46.

Beispiel 1example 1

900 ml Natronwasserglas HK 30 wurden mit 30 ml enthärtetem Wasser, 20 ml einer 41 %igen Kaliummetaboratlösung (Dichte = 1,493 g/cm3) und 50 ml einer 40%igen Glyoxallösung (Dichte = 1,270 g/cm3) zu 1000 ml Injektionslösung gemischt. Diese anwendungsfertige Silikatlösung hatte 19,85 % SiO2 und 0,41 % B203, das ergibt ein Mol-Verhältnis Si02 : B203 von 55,7.900 ml of HK 30 sodium water glass were mixed with 30 ml of softened water, 20 ml of a 41% potassium metaborate solution (density = 1.493 g / cm 3 ) and 50 ml of a 40% glyoxal solution (density = 1.270 g / cm 3 ) to give 1000 ml of solution for injection . This ready-to-use silicate solution had 19.85% SiO 2 and 0.41% B 2 0 3 , which gives a molar ratio Si0 2 : B 2 0 3 of 55.7.

Die Gelierzeit, gemessen mit dem Magnetrührer, betrug 40 min, die Druckfestigkeit des Prüfkörpers 207 N/cm2. Im Vergleich dazu ergab ein metaboratfreier Ansatz: 900 ml Natronwasserglas HK 30, gemischt mit 50 ml enthärtetem Wasser und 50 ml einer 40 %igen Glyoxallösung, gemessen mit dem Magnetrührer, eine Gelierzeit von 21 min und eine Druckfestigkeit des Prüfkörpers von 202 N/cm2. Die metaboratfreie Injektionslösung hatte keine für die Praxis ausreichende Gelierzeit.The gelling time, measured with a magnetic stirrer, was 40 min, the compressive strength of the test specimen was 207 N / cm 2 . In comparison, a metaborate-free batch resulted in: 900 ml HK 30 sodium water glass, mixed with 50 ml softened water and 50 ml of a 40% glyoxal solution, measured with a magnetic stirrer, a gelling time of 21 min and a pressure resistance of the test specimen of 202 N / cm 2 . The metaborate-free solution for injection did not have a gelation time that was sufficient in practice.

Beispiel 2Example 2

700 ml Natronwasserglas 37/40 wurden mit 186,5 ml enthärtetem Wasser, 33,5 ml einer 41 %igen Kaliummetaboratlösung (Dichte = 1,493 g/cm3) und 80 ml einer 40 %igen Glyoxallösung (Dichte = 1,270 g/cm3) zu 1000 ml Injektionslösung gemischt. Diese anwendungsfertige Injektionslösung hatte 19,63 % Si02 und 0,68 % B203 und damit ein Mol-Verhältnis SiO2 : B203 von 33,6.700 ml of sodium water glass 37/40 were mixed with 186.5 ml of softened water, 33.5 ml of a 41% potassium metaborate solution (density = 1, 49 3 g / cm 3 ) and 80 ml of a 40% glyoxal solution (density = 1.270 g / cm 3 ) mixed to 1000 ml solution for injection. This ready-to-use injection solution had 19.63% Si0 2 and 0.68% B 2 0 3 and thus a SiO 2 : B 2 0 3 molar ratio of 33.6.

Die Gelierzeit, gemessen mit dem Magnetrührer, betrug 43 min, die Druckfestigkeit des Prüfkörpers 272 N/cm2. Im Vergleich dazu ergab der metaboratfreie Ansatz aus 700 ml Natronwasserglas 37/40, 220 ml enthärtetem Wasser und 80 ml der 40 %igen Glyoxallösung eine Gelierzeit von 16 min und eine Druckfestigkeit des Prüfkörpers von 251 N/cm2. Auch bei dieser metaboratfreien Injektionslösung war die Gelierzeit für Praxiszwecke nicht ausreichend.The gelling time, measured with a magnetic stirrer, was 43 min, the compressive strength of the test specimen was 272 N / cm2. In comparison, the metaborate-free mixture of 700 ml of 37/40 sodium water glass, 220 ml of softened water and 80 ml of the 40% glyoxal solution gave a gel time of 16 min and a compressive strength of the test specimen of 251 N / cm 2 . The gelling time for this metaborate-free injection solution was not sufficient for practical purposes.

Beispiel 3Example 3

Es wurden 900 ml Natronwasserglas HK 30 mit 35 ml enthärtetem Wasser, 30 ml einer 41 %igen Kaliummetaboratlösung (Dichte = 1,493 g/cm3) und 35 ml einer technischen Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France, Dichte = 1,41 g/cm3) zu 1000 ml Injektionslösung gemischt. Diese anwendungsfertige Injektionslösung hatte 19,76 % Si02 und 0,62 % B2O3 und damit ein Mol-Verhältnis Si02 : B2O3 von 37.900 ml of HK 30 sodium water glass with 35 ml of softened water, 30 ml of a 41% potassium metaborate solution (density = 1.493 g / cm 3 ) and 35 ml of a technical glyoxal solution (Glyfix CS 50 from Hoechst France, density = 1.41 g / cm3) mixed to 1000 ml solution for injection. This ready-to-use injection solution had 19.76% Si0 2 and 0.62% B 2 O 3 and thus a molar ratio Si0 2 : B 2 O 3 of 37.

Die Gelierzeit betrug 44 min, die Druckfestigkeit des Prüfkörpers 205 W/cm2. Im Vergleich dazu ergab sich bei einer metaboratfreien Injektionslösung aus 900 ml Natronwasserglas HK 30, 65 ml enthärtetem Wasser und 35 ml technischer Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France, Dichte = 1,41 g/cm3) eine Gelierzeit von 20 min und eine Druckfestigkeit des Prüfkörpers von 200 N/cm2. Die Gelierzeit der metaboratfreien Injektionslösung reichte für Praxiszwecke nicht aus.The gelling time was 44 min, the compressive strength of the test specimen was 205 W / cm 2 . In comparison with this, a gelling time of 20 minutes resulted in a metaborate-free injection solution made from 900 ml HK 30 sodium water glass, 65 ml softened water and 35 ml technical glyoxal solution (Glyfix CS 50 from Hoechst France, density = 1.41 g / cm 3 ) and a compressive strength of the test specimen of 200 N / cm 2 . The gel time of the metaborate-free injection solution was not sufficient for practical purposes.

Beispiel 4Example 4

Aus 700 ml Natronwasserglas 37/40, 200 ml enthärtetem Wasser, 40 ml einer 41 %igen Kaliummetaboratlösung (Dichte = 1,493 g/cm3) und 60 ml einer technischen Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France, Dichte = 1,41 g/cm3) wurden 1000 ml Injektionslösung hergestellt. Diese anwendungsfertige Injektionslösung hatte 19,54 % Si02 und 0,81 % B2O3 und damit ein Molverhältnis Si02 : B203 von 28.From 700 ml of sodium water glass 37/40, 200 ml of softened water, 40 ml of a 41% potassium metaborate solution (density = 1.493 g / cm 3 ) and 60 ml of a technical glyoxal solution (Glyfix CS 50 from Hoechst France, density = 1.41 g / cm 3 ) 1000 ml solution for injection were prepared. This ready-to-use injection solution had 19.54% Si0 2 and 0.81% B 2 O 3 and thus a molar ratio Si0 2 : B 2 0 3 of 28.

Die Gelierzeit betrug 39 min und die Druckfestigkeit des Prüfkörpers 264 N/cm2. Im Vergleich dazu hatte eine metaboratfreie Injektionslösung aus 700 ml Natronwasserglas 37/40, 240 ml enthärtetem Wasser und 60 ml technischer Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France, Dichte = 1,410 g/cm3) eine Gelierzeit von 16 min und eine Druckfestigkeit des Prüfkörpers von 248 N/cm2. Auch hier reicht die Gelierzeit für Praxisanwendungen nicht aus.The gelling time was 39 min and the compressive strength of the test specimen was 264 N / cm 2 . In comparison, a metaborate-free injection solution consisting of 700 ml sodium water glass 37/40, 240 ml softened water and 60 ml technical glyoxal solution (Glyfix CS 50 from Hoechst France, density = 1.410 g / cm 3 ) had a gel time of 16 min and a pressure resistance of the test specimen of 248 N / cm 2 . Here too, the gelling time is not sufficient for practical applications.

Beispiel 5Example 5

. Aus 700 ml Natronwasserglas 37/40, 197,7 ml enthärtetem Wasser, 42,3 ml einer 32,9 %igen Natriummetaboratlösung (Dichte = 1,413 g/cm3) und 60 ml technischer Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France, Dichte = 1,41 g/cm3) wurden 1000 ml Injektionslösung hergestellt. Sie enthielt 19,57 % Si02 und 0,81 % B2O3 und hatte ein Molverhältnis Si02 : B203 von 28.. From 700 ml of sodium water glass 37/40, 197.7 ml of softened water, 42.3 ml of a 32.9% sodium metaborate solution (density = 1.413 g / cm 3 ) and 60 ml of technical glyoxal solution (Glyfix CS 50 from Hoechst France, Density = 1.41 g / cm 3 ) 1000 ml solution for injection were prepared. It contained 19.57% Si0 2 and 0.81% B 2 O 3 and had a molar ratio Si0 2 : B 2 0 3 of 28.

Die Gelierzeit dieser Injektionslösung betrug 42 min, die Druckfestigkeit des Prüfkörpers 260 N/cm2.The gel time of this injection solution was 42 min, the compressive strength of the test specimen was 260 N / cm 2 .

Beispiel 6Example 6

Aus 700 ml Natronwasserglas 37/40, 198,7 ml enthärtetem Wasser, 21,2 ml einer 32,9 %igen Natriummetaboratiösung (Dichte = 1,413 g/cm3), 20,1 ml einer 41 %igen Kaliummetaboratlösung (Dichte = 1,493 g/cm3) und 60 ml technischem Glyoxal (Glyfix CS 50 der Fa. Hoechst France, Dichte - 1,41 g/cm3) wurden 1000 ml Injektionslösung hergestellt. Sie enthielt 19,55 % Si02 und 0,81 % B20a und hatte ein Molverhältnis Si02 : B2O3 von 28.From 700 ml of sodium water glass 37/40, 198.7 ml of softened water, 21.2 ml of a 32.9% sodium metaborate solution (density = 1.413 g / cm3), 20.1 ml of a 41% potassium metaborate solution (density = 1.493 g / cm 3 ) and 60 ml technical glyoxal (Glyfix CS 50 from Hoechst France, density - 1.41 g / cm 3 ) 1000 ml solution for injection were prepared. It contained 19.55% Si0 2 and 0.81% B 2 0 a and had a molar ratio Si0 2 : B 2 O 3 of 28.

Die Gelierzeit betrug 37 min, die Druckfestigkeit des Prüfkörpers betrug 262 N/cm2.The gel time was 37 min, the compressive strength of the test specimen was 262 N / cm 2 .

Beispiel 7Example 7

Aus 900 ml Natronwasserglas HK 30, 34,1 ml enthärtetem Wasser, 15,0 ml einer 41 %igen Kaliummetaboratlösung (Dichte = 1,493 g/cm3), 15,9 ml einer 32,9 %igen Natriummetaboratlösung (Dichte = 1,413 g/cm3) und 35 ml einer technischen Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France, Dichte = 1,41 g/cm3) wurden 1000 ml Injektionslösung hergestellt. Sie enthielt 19,77 % Si02 und 0,62 % B203. Daraus resultiert ein Molverhältnis Si02 : B2O3 von 37.From 900 ml HK 30 sodium water glass, 34.1 ml softened water, 15.0 ml of a 41% potassium metaborate solution (density = 1.493 g / cm 3 ), 15.9 ml of a 32.9% sodium metaborate solution (density = 1.413 g / cm 3 ) and 35 ml of a technical glyoxal solution (Glyfix CS 50 from Hoechst France, density = 1.41 g / cm 3 ) 1000 ml solution for injection were prepared. It contained 19.77% Si0 2 and 0.62% B 2 0 3 . This results in a molar ratio of Si0 2 : B 2 O 3 of 37.

Die Gelierzeit dieser Lösung betrug 45 min, die Druckfestigkeit des Prüfkörpers 204 N/cm2.The gel time of this solution was 45 min, the compressive strength of the test specimen was 204 N / cm 2 .

Die drei folgenden Vergleichsbeispiele sollen belegen, daß die gewünschte Gelierzeitverlängerung durch Verwendung nichtbeanspruchter Borate oder einfacher Basen, wie Kalilauge oder Triethanolamin, nicht erreicht wird.The following three comparative examples are intended to demonstrate that the desired extension of the gelation time is not achieved by using unused borates or simple bases such as potassium hydroxide solution or triethanolamine.

Vergleichsbeisaiel 1Comparative example 1

Aus 700 ml Natronwasserglas 37/40, 193 ml enthärtetem Wasser, 47 ml einer 29,2 %igen Kaliumtetraboratlösung (Dichte = 1,279 g/cm3) und 60 ml technischer Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) wurden 1000 ml Injektionslösung hergestellt. Sie enthielt 19,64 % SiO2 und 0,82 % B203. Daraus resultiert ein Molverhältnis Si02 : B2O3 von 28.From 700 ml of sodium water glass 37/40, 193 ml of softened water, 47 ml of a 29.2% potassium tetraborate solution (density = 1.279 g / cm 3 ) and 60 ml of technical glyoxal solution (Glyfix CS 50 from Hoechst France) became 1000 ml solution for injection produced. It contained 19.64% SiO 2 and 0.82% B 2 0 3 . This results in a molar ratio of Si0 2 : B 2 O 3 of 28.

Die Gelierzeit dieser Injektionslösung betrug 20 min und war damit nicht ausreichend für den Praxiseinsatz.The gel time of this injection solution was 20 min and was therefore not sufficient for practical use.

Veraleichsbeispiel 2Comparison example 2

700 ml Natronwasserglas 37/40 wurden mit 200,5 ml enthärtetem Wasser, 39,5 ml einer 28 %igen Kalilauge (Dichte 1,269 g/cm3) und 60 ml einer technischen Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) zu 1000 ml Injektionslösung gemischt. Sie enthielt 19,68 % Si02.700 ml of sodium water glass 37/40 were mixed with 200.5 ml of softened water, 39.5 ml of a 28% potassium hydroxide solution (density 1.269 g / cm 3 ) and 60 ml of a technical glyoxal solution (Glyfix CS 50 from Hoechst France) ml of solution for injection mixed. It contained 19.68% Si0 2 .

Die Gelierzeit betrug 21 min und war damit nicht ausreichend für den Praxiseinsatz. Ein Prüfkörper war nicht herstellbar, da nur Weichgel entstand.The gel time was 21 minutes and was therefore not sufficient for practical use. A test specimen could not be produced because only soft gel was produced.

Vergleichsbeispiel 3Comparative Example 3

700 ml Natronwasserglas 37/40 wurden mit 210 ml enthärtetem Wasser, 30 ml einer 20 %igen Triethanolaminlösung (Dichte = 1,032 g/cm3) und 60 ml einer technischen Glyoxallösung (Glyfix CS 50 der Fa. Hoechst) zu 1000 ml Injektionslösung gemischt. Die Lösung enthielt 19,82 % SiO2 und 0,49 % Triethanolamin.700 ml of sodium water glass 37/40 were mixed with 210 ml of softened water, 30 ml of a 20% triethanolamine solution (density = 1.032 g / cm 3 ) and 60 ml of a technical glyoxal solution (Glyfix CS 50 from Hoechst) to 1000 ml solution for injection. The solution contained 19.82% SiO 2 and 0.49% triethanolamine.

Die Gelierzeit der Injektionslösung betrug 14 min und war damit nicht ausreichend für den Praxiseinsatz.The gel time of the injection solution was 14 min and was therefore not sufficient for practical use.

Veraleichsbeispiel 4Comparison example 4 Bestimmung des chemischen Sauerstoffbedarfs ICSB-WertlDetermination of chemical oxygen demand ICSB value

Es wurden vergleichende Bestimmungen des CSB-Wertes an Prüfkörpem durchgeführt, die einerseits mit dem Mittel gemäß der Erfindung und andererseits mit einem solchen gemäß dem Stand der Technik hergestellt worden waren.Comparative determinations of the COD value were carried out on test specimens which were produced on the one hand with the agent according to the invention and on the other hand with one according to the prior art.

Die Herstellung der Prüfkörper erfolgte analog den allgemeinen Angaben vor Beispiel 1. Die verwendeten Injektionslösungen entsprachen:

  • (a) Beispiel 3 gemäß der Erfindung,
  • (b) einer Wasserglaslösung mit einem Härtergemisch gemäß dem Stand der Technik - entsprechend den nachstehenden Angaben:
  • 57,45 ml Natronwasserglas 37/40 wurden mit 11,9 ml enthärtetem Wasser und 9,69 ml eines Dicarbonsäureester-Gemisches (Durcisseur® 1000 der Fa. Rhöne Poulenc) bei Raumtemperatur (21-22°C) gemischt.
The test specimens were produced analogously to the general information given in Example 1. The injection solutions used corresponded to:
  • (a) Example 3 according to the invention,
  • (b) a water glass solution with a hardener mixture according to the prior art - according to the following information:
  • 57.45 ml of sodium water glass 37/40 were mixed with 11.9 ml of softened water and 9.69 ml of a dicarboxylic acid ester mixture (Durcisseur® 1000 from Rhönen Poulenc) at room temperature (21-22 ° C.).

Die Zusammensetzung der verwendeten Injektionslösungen war so gewählt, daß vergleichbare Gelzeiten und Festigkeiten der Prüfkörper resultierten.The composition of the injection solutions used was chosen so that comparable gel times and strengths of the test specimens resulted.

Die so erhaltenen Prüfkörper wurden - nach sieben Tagen Lagerung unter Luftabschluß - jeweils in einen 1 I-Polybecher auf ein gelochtes VA-Stahlpodest (I = 55 mm, h = 20 mm) gestellt. Anschließend wurden 900 ml dest. H20 zugegeben, der Polybecher verschlossen und das Wasser mit Hilfe eines Magnetrührwerkes (Einstellstufe 5 - 7) gerührt.The test specimens thus obtained were each placed in a 1 liter poly beaker on a perforated VA steel platform (I = 55 mm, h = 20 mm) after storage for seven days in the absence of air. Then 900 ml of dist. H 2 0 added, the poly beaker closed and the water stirred with the aid of a magnetic stirrer (setting levels 5 - 7).

Die Entnahme von Eiuat-Proben (jeweils 50 ml der Eluate) aus den Polybechem erfolgte nach 1 Stunde, 8 Stunden, 24 Stunden und nach 3 Tagen, ohne Auffüllen der Ausgangslösung.Egg samples (50 ml each of the eluates) were removed from the polybechem after 1 hour, 8 hours, 24 hours and after 3 days, without replenishing the starting solution.

Die Bestimmung des chemischen Sauerstoffbedarfs in mg O2/I erfolgte nach Dr. Lange Küvettentest LCK 114 (für 150 mg bis 1000 mg O2/l) (Fa. Dr. Bruno Lange GmbH, Berlin).The chemical oxygen demand in mg O 2 / I was determined according to Dr. Long cuvette test LCK 114 (for 150 mg to 1000 mg O 2 / l) (Dr. Bruno Lange GmbH, Berlin).

Die erhaltenen Werte sind der folgenden Tabelle zu entnehmen.

Figure imgb0001
Die erhaltenen CSB-Werte zeigen, daß die Verwendung der erfindungsgemäßen Injektionslösung zu wesentlich geringeren Werten - und damit zu einer wesentlich geringeren Belastung des Grundwassers bzw. des Bodens - führt, als die Verwendung von Injektionslösungen gemäß dem Stand der Technik.The values obtained are shown in the following table.
Figure imgb0001
 The COD values obtained show that the use of the injection solution according to the invention leads to significantly lower values - and thus to a significantly lower contamination of the groundwater or the soil - than the use of injection solutions according to the prior art.

II Zur Verfestiauna und Abdichtuna von mineralischen BaustoffenII For hardening and sealing of mineral building materials

Bei der Abdichtung von mineralischen Baustoffen, z.B. von Mauerwerk, ist ebenfalls eine lange Gelierzeit bei möglichst hohem Feststoffgehalt erwünscht. Dadurch dringt die Lösung stärker in das Mauerwerk ein und führt zu dem erforderlichen Effekt.When sealing mineral building materials, e.g. of masonry, a long gel time with the highest possible solids content is also desirable. As a result, the solution penetrates more into the masonry and leads to the required effect.

Für die Beispiele 8 bis 11 wurde das Kaliwasserglas 28/30 mit einem Si02-Gehalt von 21,04 %, dem K20-Gehalt von 8,23 %, der Dichte 1256 kg/m3 und der Viskosität von 44 mPas verwendet. Dichte und Viskosität wurden bei 20°C gemessen, das Molverhältnis Si02 : K20 betrug 4,01.Potassium water glass 28/30 with an SiO 2 content of 21.04%, a K 2 0 content of 8.23%, a density of 1256 kg / m 3 and a viscosity of 44 mPas was used for Examples 8 to 11 . Density and viscosity were measured at 20 ° C, the molar ratio Si0 2 : K 2 0 was 4.01.

Beispiel 8Example 8

140 g Kaliwasserglas 28/30 wurden mit 51,5 g enthärtetem Wasser, 0,5 g 41 %iger Kaliummetaboratlösung (Dichte = 1,493 g/cm3)und 8 g technischer Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) zu 200 g Injektionslösung gemischt. Sie enthielt 14,73 % Si02 und 0,044 % B2O3, das Molverhältnis Si02 : B203 betrug 388. Die Gelierzeit betrug 30 min.140 g of potassium water glass 28/30 were mixed with 51.5 g of softened water, 0.5 g of 41% potassium metaborate solution (density = 1.493 g / cm 3 ) and 8 g of technical glyoxal solution (Glyfix CS 50 from Hoechst France) to 200 g Solution for injection mixed. It contained 14.73% Si0 2 and 0.044% B 2 O 3 , the molar ratio Si0 2 : B 2 0 3 was 388. The gel time was 30 min.

Beispiel 9Example 9

140 g Kaliwasserglas 28/30 wurden mit 51 g enthärtetem Wasser, 1 g 41 %iger Kaliummetaboratlösung (Dichte = 1,493 g/cm3) und 8 g technischer Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) zu 200 g Injektionslösung gemischt. Diese enthielt 14,73 % Si02 und 0,088 % B2O3 und hatte ein Molverhältnis Si02 : B2O3 von 194. Die Gelierzeit dieser Injektionslösung betrug 37 min.140 g of 28/30 potassium water glass were mixed with 51 g of softened water, 1 g of 41% potassium metaborate solution (density = 1.493 g / cm3) and 8 g of technical glyoxal solution (Glyfix CS 50 from Hoechst France) to give 200 g of solution for injection. This contained 14.73% Si0 2 and 0.088% B 2 O 3 and had a molar ratio Si0 2 : B 2 O 3 of 194. The gel time of this injection solution was 37 min.

Beispiel 10Example 10

140 g Kaliwasser 28/30 wurden mit 43 g enthärtetem Wasser, 9 g einer 41 %igen Kaliummetaboratlösung (Dichte = 1,493 g/cm3) und 8 g einer technischen Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) zu 200 g Injektionslösung gemischt. Sie enthielt 14,73 % Si02 und 0,78 % B203, das Molverhältnis SiO2 : B203 betrug 21,8.140 g of potassium water 28/30 were mixed with 43 g of softened water, 9 g of a 41% potassium metaborate solution (density = 1.493 g / cm 3 ) and 8 g of a technical glyoxal solution (Glyfix CS 50 from Hoechst France) to give 200 g of injection solution . It contained 14.73% Si0 2 and 0.78% B 2 0 3 , the molar ratio SiO 2 : B 2 0 3 was 21.8.

Die Gelierzeit ergab sich zu 210 min.The gelling time was 210 min.

Vergleicht man die Gelierzeiten der mit steigendem Metaboratanteil versehenen Injektionslösungen mit einer metaboratfreien Injektionslösungen aus 140 g Kaliwasserglas 28/30, 52 g enthärtetem Wasser und 8 g technischer Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France), so ergibt sich für die letztere eine vergleichsweise niedrige Gelierzeit von 23 min.If you compare the gelling times of the injection solutions with increasing metaborate content with a metaborate-free injection solution made from 140 g 28/30 potassium water glass, 52 g softened water and 8 g technical glyoxal solution (Glyfix CS 50 from Hoechst France), the latter is comparatively similar low gel time of 23 min.

Beispiel 11Example 11

120 g Kaliwasserglas 28/30 wurden mit 65 g enthärtetem Wasser, 8 g einer 41 %igen Kaliummetaboratlösung (Dichte = 1,493 g/cm3) und 7 g einer technischen Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) zu 200 g Injektionslösung gemischt. Sie enthielt 12,62 % Si02 und 0,7 % B203, das Molverhältnis Si02 : B203 betrug 20,9.120 g of 28/30 potassium water glass were mixed with 65 g of softened water, 8 g of a 41% potassium metaborate solution (density = 1.493 g / cm 3 ) and 7 g of a technical glyoxal solution (Glyfix CS 50 from Hoechst France) to give 200 g of injection solution . It contained 12.62% Si0 2 and 0.7% B 2 0 3 , the molar ratio Si0 2 : B203 was 20.9.

Diese Injektionslösung hatte eine Gelierzeit von 8 h und kann damit während einer Arbeitsschicht voll ein gesetzt werden. Im Vergleich dazu hat die metaboratfreie Injektionslösung aus 120 g Kaliwasserglas 28/30, 73 g enthärtetem Wasser, und 7 g technischer Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) eine Gelierzeit von 40 min.This solution for injection had a gel time of 8 hours and can therefore be used fully during a work shift. In comparison, the metaborate-free injection solution made from 120 g 28/30 potassium water glass, 73 g softened water, and 7 g technical glyoxal solution (Glyfix CS 50 from Hoechst France) has a gel time of 40 min.

III Zur Herstellung von Bindemitteln für mineralische FormkörperIII For the production of binders for mineral moldings

Der Einsatz von silikatischen Bindemitteln in Gießereien ist bekannt. Gewünscht wird ein Bindemittel, das in der Vormischung möglichst lange offene Zeiten hat, die aber fallweise auch unter 30 min liegen können. In den Beispielen 12 bis 14 wurden eingesetzt Natronwasserglas 48/50, mit 33,41 % Si02, 12,11 % Na2O, einem Molverhhältnis Si02 : Na20 = 2,84, einer Dichte von 1518 kg/m3 und einer Viskosität von 2263 mPas (20°C) und Natronwasserglas 43/45 mit 31,36 % Si02, 10,17 % Na20, einem Molverhältnis Si02 : Na20 = 3,18, einer Dichte von 1449 kg/m3 (20°C) und einer Viskosität von 975 mPas (20°C).The use of silicate binders in foundries is known. A binder is desired which has open times in the premix that are as long as possible, but which can occasionally be less than 30 minutes. In Examples 12 to 14 sodium water glass 48/50, with 33.41% Si0 2 , 12.11% Na 2 O, a molar ratio Si0 2 : Na 2 0 = 2.84, a density of 1518 kg / m3 and was used a viscosity of 2263 mPas (20 ° C) and soda water glass 43/45 with 31.36% Si0 2 , 10.17% Na 2 0, a molar ratio Si0 2 : Na 2 0 = 3.18, a density of 1449 kg / m 3 (20 ° C) and a viscosity of 975 mPas (20 ° C).

Beisoiel 12Example 12

100 g Natronwasserglas 48/50 wurden gemischt mit 10 g enthärtetem Wasser, 4,1 g Kaliummetaborat und 13,4 g einer technischen Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) zu 127,5 g Bindemittel mit 26,2 % Si02 und 1,39 % B203. Das Bindemittel hatte ein Molverhaltnis Si02 : B203 von 21,9. Die Gelierzeit betrug 10 min. Im Vergleich dazu ergab das metaboratfreie Bindemittel aus 100 g Natronwasserglas 48/50, 10 g enthärtetem Wasser und 13,4 g technischer Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) nur eine Gelierzeit von 5,5 min.100 g of sodium water glass 48/50 were mixed with 10 g of softened water, 4.1 g of potassium metaborate and 13.4 g of a technical glyoxal solution (Glyfix CS 50 from Hoechst France) to 127.5 g of binder with 26.2% SiO 2 and 1.39% B 2 0 3 . The binder had a molar ratio Si0 2 : B 2 0 3 of 21.9. The GE time was 10 min. In comparison, the metaborate-free binder from 100 g soda water glass 48/50, 10 g softened water and 13.4 g technical glyoxal solution (Glyfix CS 50 from Hoechst France) only gave a gel time of 5.5 min.

Beisaiel 13Example 13

100 g Natronwasserglas 43/45 wurden gemischt mit 10 g enthärtetem Wasser, 8,2 g Kaliummetaborat und 12 g einer technischen Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) zu 130,2 g Bindemittel mit 24,1 % Si02 und 2,67 % B203. Das Bindemittel hatte ein Molverhältnis Si02 : B203 von 10,5 und eine Gelierzeit von 18 min. Im Vergleich dazu ergab ein metaborattreier Ansatz aus 100 g Natronwasserglas 43/45, 10 g enthärtetem Wasser und 12 g technischem Glyoxal (Glyfix CS 50 der Fa. Hoechst France) eine Gelierzeit von 5,5 min.100 g of soda water glass 43/45 were mixed with 10 g of softened water, 8.2 g of potassium metaborate and 12 g of a technical glyoxal solution (Glyfix CS 50 from Hoechst France) to 130.2 g of binder with 24.1% Si0 2 and 2 , 67% B 2 0 3 . The binder had a molar ratio Si0 2 : B 2 0 3 of 10.5 and a gel time of 18 min. In comparison, a metaborate-free batch consisting of 100 g of sodium water glass 43/45, 10 g of softened water and 12 g of technical glyoxal (Glyfix CS 50 from Hoechst France) gave a gel time of 5.5 min.

Beispiel 14Example 14

100 g Natronwasserglas 43/45 wurden gemischt mit 5 g enthärtetem Wasser, 12,3 g Kaliummetaborat und 14,1 g einer technischen Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) zu 131,4 g Bindemittel mit einem Si02-Gehalt von 23,87 % und einem B203-Gehalt von 3,98 %. Das Bindemittel hatte ein Mol- verhältnis Si02 : B203 von 7 und eine Gelierzeit von 18 min. Im Vergleich dazu ergab der metaboratfreie Ansatz aus 100 g Natronwasserglas 43/45, 5 g enthärtetem Wasser und 14,1 g technischer Glyoxallösung (Glyfix CS 50 der Fa. Hoechst France) eine Gelierzeit von 3,5 min.100 g of sodium water glass 43/45 were mixed with 5 g of softened water, 12.3 g of potassium metaborate and 14.1 g of a technical glyoxal solution (Glyfix CS 50 from Hoechst France) to 131.4 g of binder with an SiO 2 content of 23.87% and a B 2 0 3 content of 3.98%. The binder had a molar ratio of SiO 2 : B 2 0 3 of 7 and a gel time of 18 min. In comparison, the metaborate-free batch consisting of 100 g of 43/45 sodium water glass, 5 g of softened water and 14.1 g of technical glyoxal solution (Glyfix CS 50 from Hoechst France) gave a gel time of 3.5 min.

Claims (11)

1. Sealing and/or stabilizing and/or binding preparations based on modified alkali metal silicate solutions, characterized in that they contain alkali metal silicate solutions with a molar ratio of Si02 to Me20 (Me = sodium or potassium) of from 2 to 4.5, sodium metaborate and/or potassium metaborate in a molar ratio of Si02 to B203 of from 5 to 400 and glyoxal.
2. Preparations as claimed in claim 1, characterized in that the Si02:Me20 molar ratios of the alkali metal silicates are from 3.0 to 4.0.
3. Preparations as claimed in claims 1 and/or 2, characterized in that the Si02:B203 molar ratio is from 7 to 60.
4. Preparations as claimed in claims 1 to 3, characterized in that the glyoxal is present in a quantity of from 0.4% by weight to 12% by weight and preferably in a quantity of from 1.5% by weight to 7% by weight.
5. Preparations as claimed in claims 1 to 4, characterized in that the Si02 concentrations are up to 30% by weight.
6. The use of the preparations claimed in claims 1 to 5 for sealing and/or stabilizing ground and soils.
7. The use of the preparations claimed in claims 1 to 5 for sealing and/or stabilizing mineral building materials.
8. The use of the preparations claimed in claims 1 to 5 for binding mineral moldings.
9. A process for sealing and/or stabilizing ground and soils, characterized in that the preparations claimed in claims 1 to 5 are used.
10. A process for sealing and/or stabilizing mineral building materials, characterized in that the preparations claimed in claims 1 to 5 are used.
11. A process for stabilizing and binding mineral moldings, characterized in that the preparations claimed in claims 1 to 5 are used.
EP86101482A 1986-02-05 1986-02-05 Sealing, consolidating and/or binding agent based on modified alcaline silicate solutions Expired - Lifetime EP0231415B1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP86101482A EP0231415B1 (en) 1986-02-05 1986-02-05 Sealing, consolidating and/or binding agent based on modified alcaline silicate solutions
AT86101482T ATE51392T1 (en) 1986-02-05 1986-02-05 AGENT BASED ON MODIFIED ALKALI METAL SILICATE SOLUTIONS FOR SEALING AND/OR CONSOLIDATING AND/OR BINDING.
DE8686101482T DE3669871D1 (en) 1986-02-05 1986-02-05 AGENT BASED ON MODIFIED ALKALINE METAL SILICATE SOLUTIONS FOR SEALING AND / OR STRENGTHENING AND / OR BINDING.
ES8700248A ES2003677A6 (en) 1986-02-05 1987-02-03 Sealing, consolidating and/or binding agent based on modified alcaline silicate solutions.
US07/011,174 US4755226A (en) 1986-02-05 1987-02-05 Sealing and/or stabilizing and/or binding preparations comprising alkali metal silicate solutions

Applications Claiming Priority (1)

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EP86101482A EP0231415B1 (en) 1986-02-05 1986-02-05 Sealing, consolidating and/or binding agent based on modified alcaline silicate solutions

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EP0231415A1 EP0231415A1 (en) 1987-08-12
EP0231415B1 true EP0231415B1 (en) 1990-03-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4033884C1 (en) * 1990-10-25 1991-10-02 Wolfgang Dipl.-Chem. Dr. 1000 Berlin De Ortlepp Strengthening of mineral by raising its electrical conductivity - by adding water glass and/or silane(s) mixed with alkaline earth salt soln., to seal minerals and protect ground water

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4863518A (en) * 1987-10-19 1989-09-05 Blount David H Production of polyol-alkali metal silicate glass emulsion
GB9501099D0 (en) * 1995-01-20 1995-03-08 Brunner Mond & Co Ltd Silicate solutions
EP0760353A1 (en) * 1995-08-30 1997-03-05 Rudolf Schanze A water glass based composition for sealing and method of hardening water glass based mass
DE19650206A1 (en) * 1996-12-04 1998-06-10 Henkel Kgaa Process for the rehabilitation of liquid-carrying underground pipelines by injecting yellow-binding waterglass solutions
JP3886938B2 (en) * 2003-06-30 2007-02-28 山田 文隆 Inorganic coating composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1166581A (en) * 1956-12-28 1958-11-13 Bozel Maletra Gel convertible into a mass having the properties of a cement and process for preparing these products
US3028340A (en) * 1956-12-28 1962-04-03 Nobel Bozel Production of new compositions from glyoxal and alkali metal silicates
US3202214A (en) * 1960-04-18 1965-08-24 Halliburton Co Preparation and use of sodium silicate gels
FR1476636A (en) * 1965-12-28 1967-04-14 Progil Gelling reagents for soluble silicates
DE2636313A1 (en) * 1976-08-12 1978-02-16 Novopan Gmbh Mineral bonded panels and mouldings mfr. - by hot pressing wood chips coated with aq. binder of water glass and borate(s)
DE2714889A1 (en) * 1977-04-02 1978-10-12 Henkel Kgaa BINDERS BASED ON ALKALINE SILICATE SOLUTIONS
US4293340A (en) * 1979-11-05 1981-10-06 Diamond Shamrock Corporation Composition and process for stabilizing soil

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4033884C1 (en) * 1990-10-25 1991-10-02 Wolfgang Dipl.-Chem. Dr. 1000 Berlin De Ortlepp Strengthening of mineral by raising its electrical conductivity - by adding water glass and/or silane(s) mixed with alkaline earth salt soln., to seal minerals and protect ground water

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US4755226A (en) 1988-07-05
EP0231415A1 (en) 1987-08-12
DE3669871D1 (en) 1990-05-03
ES2003677A6 (en) 1988-11-01
ATE51392T1 (en) 1990-04-15

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